Compositions of vinyl chloride resins and graft copolymers of acrylonitrile-type monomer compositions upon diene polymers and articles formed therefrom



Aug. 13, 1957 R. A. HAYES 2,802,309

COMPOSITIONS OF VINYL CHLORIDE RESINS AND CRAFT COPOLYMERS 0FACRYLONITRILETYPE MUNOMER COMPOSITIONS UPQN DIENE POLYMERS AND ARTICLESFORMED THEREFROM Filed NOV. 50, 1955 Sivaama,

ALPHA METHYL STYREME m2 Mnnum: Tuzlzzor ACEYLOHFTQILE, lfioBuTYLsu:

METHACRYLON 112 1 LE 02 M \xTuRc. THEREOF 1N VEN TQR.

BY 7AM 2,802,899 Patented Aug. 13, 1957 amass:

COMPOSITIONS OF VINYL CHLORIDE RESINS AND GRAFT COPOLYMERS OF ACRYLONI-TRlLE-TYPE MONOMER COMPOSITIONS UPON DIENE POLYMERS AND ARI'ICLES FORMEDTHEREFROM Robert A. Hayes, Akron, Ohio, assignor to 'i'he Firestone Tire& Rubber Company, Akron, Ohio, a corporation of Ohio ApplicationNovember 30, 1953, Serial No. 394,958

21 Claims. (Cl. 260-455) This invention relates to polyvinyl chloridecompositions having greatly improved impact strengths. In general, thecompositions of this invention comprise (A) vinyl chloride resinsblended with (B) graft copolymers of mixtures of styrene andacrylonitrile or their equivalents upon diene rubber substrates. As usedin the present specification, and as defined in the Report onNomenclature of the International Union of Pure and Applied Chemistry,Journal of High Polymer Science, vol. VIII, p. 260, the term graftcopolymcr of a mixture of styrene and acrylonitrile upon a diene rubbersignifies a polymeric product produced by subjecting a mixture ofstyrene and acrylonitrile or their equivalents to polymerizingconditions in the presence of a previously polymerized diene rubber, asmore fully described hereinafter.

A highly successful development in the vinyl chloride resin field hasbeen the use of these resins in unplasticized or only slightlyplasticized form as moldings, piping, sheets and the like. Thesematerials are easily fabricated and have outstanding resistance tochemical attack, as a consequence of which they have come into extensiveuse in the chemical and process industries. Unplasticized vinyl chlorideresins are rather brittle, however, and this deficiency has limitedtheir use to situations where shock and impact loads are notencountered. Attempts to improve the impact strength of polyvinylchloride by incorporation of plasticizers, butadiene-acrylonitrilerubbers, and like compounding ingredients have been unsuccessful,because the improvement in impact strength obtained in this way hasentailed an undue sacrifice of other properties, particularly heatdistortion temperature.

Accordingly, it is an object of this invention to provide novel vinylchloride resin compositions having improved properties.

Another object is to provide rigid vinyl chloride resin compositionshaving greatly improved impact strength.

A further object is to provide such compositions which will haveimproved impact strength without sacrificing the other desirableproperties thereof.

Still another object is to provide rigid vinyl chloride resincompositions having both high heat distortion temperature and highimpact strengths.

The invention will be described in connection with the accompanyingdrawing; which is a trilinear composition diagram showing theproportions of monomers to be included in a graft copolymer to be usedin practicing the invention.

SYNOPSIS OF THE INVENTION 1 Based on the total weight of theconstituents (A) and (B),

Hereinafter, for brevity, the mixture (B) will be desig nated astyreneacryonitrile-type mixture. The ingredients (A) and (B) should inturn constitute at least 50% of the entire composition, the balancebeing made up of conventional fillers, pigments, reinforcing agents,plasticizers and the like. In a preferred embodiment of the invention,in which the compositions are in rigid, unplasticized form, anyplasticizers or other resin-soluble ingredients should constitute notmore than 10% by weight of the resin plus such resin-solubleingredients. The compositions have impact strengths, both at high andlow temperatures, far superior to comparable vinyl chloride resinsheretofore prepared; and in all other relevant properties, notablymodulus of elasticity, hardness and heat distortion temperatures, thecompositions are fully equal to conventional polyvinyl chloridecompositions.

The graft copolymers of styren -armylonitrile-Iype 0r styreneisobutylene acrylonitrile type mixtures upon rubbery diene polymers andcopolymers These are materials produced by adding monomericstyreneacrylonitrile-type mixtures to an already completely or nearlycompletely free-radical-polymerized latex of a diene rubber, whichlatter material will be more fully discussed hereinbelow. Polymerizationby freeradical mechanisms is then continued. In the resultant product,the monomers in the styrene-acrylonitrile mixture appear to havecombined with the already poly merized diene rubber; at any rate, onlysmall amounts of the polymers or copolymers which would result from thestyrene-acrylonitriie mixture can be separated therefrom by physicalmethods. Such products are referred to in this specification as graftcopolymers of styreneacrylonitriletype mixtures upon the diene rubbers.Without absolute commitment to this theory, it is believed that centersalong the chains of already polymerized dienc rubber in the originallatex are reactivated and serve to start new branching side-chains ofpolymerized monomers from the styrcne-acrylonitrile mixture attached tothe old dicne rubber polymer chains.

With reference to the styrene-acrylonitrilc-type mixture of monomers tobe graft copolymerized upon the diene rubber, these are mixtures of (I)Styrene, alpha-methyl styrene,

isobutylene, or a mixture of any of Within the limits these within therange of proporof compositions tions set forth below bounded by the plusq u a d rilateral (ll) Acrylonitrile or methacrylo- PQRS on the nitrileor a mixture of these in any drawing.

proportion The styrene and alphamethyl styrene of the ingredients (I)are fully interchangeable with each other, and the acrylonitrile andmethacrylonitrile of ingredients (II) are fully interchangeable witheach other, in the practice of this invention. However, theincorporation of isobutylenc necessitates an adjustment of the limitswithin which the ingredients (I) on the one hand, and the in gredicnts(II) on the other hand, may be mixed. These relationships are shown inthe trilinear chart of the drawing, wherein the quadrilateral PQRSencloses the area representing compositions operative in this invention.The coordinates of the vertices of the quadrilateral PQRS are asfollows.

With reference to the dicnc rubber latex upon which thestyrene-acrylonitrile-type mixture or their ho-mologs is to be graftcopolymerized, this may be a latex of a synthetic rubber havingpolymerized therein the following monomers in the following proportions.

Percent Butadiene, isoprcne, or a mixture thereof in any proportion60-100 Acrylonitrile, alpha-methyl acrylonitrile, styrene, alpha-methylstyrene or a mixture of any of these in any proportion 40 Othernon-cross-linking monomers copolymerizable with butadiene and isoprene010 Other cross-linking monomers copolymerizable with butadienc andisoprene 0-30 The percentages are based on the weight of the rubbercontained in the latex and are chosen so as to add up to 100%. Therubbers are essentially the synthetic diene rubbers of commerce, i. e.,butadiene or isoprene rubbers, with or without the addition ofsubstantial but minor proportions of acrylonitrile, methacrylonitrilc,styrene or methyl styrene. The other non-cross-linking monomers andcross-linking monomers do not alter the essential natures of theserubbers. Suitable cross-linking monomers include for instancenon-conjugated ethylenically doublyunsaturated compounds such as divinylbenzene. Suitable non-cross-linking comonomers include monoethylenic andconjugated diethylcnic unsaturated compounds such as, for instance,vinyl compounds on the order of vinyl acetate, vinyl formate, vinylpropionate, higher fatty vinyl esters such as vinyl stearate, vinylchloride, vinyl fluoride and the like; vinyl aromatics such as thevarious monoand poly-nuclcarly-chlorinated styrenes, vinyl naphthalene,vinyl carbazole and the like; vinyl ethers and ketones such as methylvinyl ether, isopropyl vinyl ether and the like; vinylidene compoundssuch as vinylidenc chloride, vinylidene ohlorobromide, methylisopropenyl kctone, isopropenyl acetate and the like; acrylic compoundssuch as acrylic acid, methacrylic acid, methyl acrylate, methylmethacrylatc, ethyl acrylate, diethyl maleate, maleic anhydride, and thelike; and conjugated unsaturated compounds such as isoprene,2,3-dirnethyl-l,3-butadione, chloroprene, piperylene,2,3-dicl1loro-l,3-butadiene and the like. For a more complete list ofcompounds known to copolymerize with butadiene and isoprene, refcrenceis made to lsirczil Kurxes Handbuch Der PolymerisationsTechnik," EdwardsErothcrs, lnc., vol. 2, p. 655, 656, the items indented under Butadicn."

The original polymerization of the latex upon which thestyrene-acrylonitrile-typc mixture is to be graft copolymerized iscarried out in accordance with any usual or suitable procedure in thisart. in general, the butadiene and/or isoprcnc, together with anycomonomers to be used, is emulsified in water with the aid ofnicelle-forming emulsifying agents which are usually compoundscontaining hydrocarbon groups of from 8 to 22 carbon atoms coupled tohighly polar solubilizing groups such as alkali metal and ammoniumcarboxylate groups, sulfate halfester groups, sulfonate groups,phosphate partial ester groups and the like. Exemplary emulsifyingagents include sodium oleate, sodium stcaratc, the sodium salts of thesulfate half esters of fatty alcohols produced by reduction of the fattyacids of natural oils such as cocoanut oil, sodium abietate, sodiumsalts of sulfosuccinic esters such as sodium dioctyl sulfosuccinate,sodium salts of alkylated benzene and naphthalene sulfonic acids such assodium didodecyl naphthalene sulfonate, sodium salts of monosulfatedfatty monoglycerides and the like. The polymerization medium willcontain a suitable water-soluble frec-radicahgencrating catalyst such ashydrogen peroxide, potassium or sodium persulfates, perboratcs,peracetates, percaroonates and the like, which catalysts may beassociated with activating systems such as redox systerns involvingversivalent metals and mild reducing agents. Generally also thepolymerization medium contains a chain-transfer agent such as a higheralkyl mercaptan on the order of dodecyl mercaptan, which both moderatesthe molecular weights of the products and also assists in initiating theaction of the catalysts in the polymerization. However, these arepreferably used in somewhat smaller quantities than is ordinarily thecase when butadiene is being polymerized to produce a general purposeelastomer, as any residual chain transfer agent may unduly retard thereaction of the styrene or alphamethyl styrene added for graftcopolymerization. Polymerization is carried out at temperatures fromabout 40 C. to C. or, in the case of the activated systems, is carriedout over a range including lower temperatures such as 0 C. to 80 C. Thepolymerization will usually be carried to a conversion of at least about75% before the monomers are added for graft copolymerization thereon.Any unreacted butadiene and/or isoprene and/or associated comonomer isoptionally, and preferably, stripped off from the latex before themonomers are added for graft copolymerization.

To the latex prepared as just described, there is added astyrene-acrylonitrile-type mixture or styrene-acrylonitrilcisobutylenetype mixture in amounts such that the total added monomers constitute atleast 10% of the combined weight of this newly added monomeric mixtureand the polymer or copolymer of butadiene and/or isoprene already in thelatex. Polymerization is continued, either under the action of thecatalyst originally supplied in the preparation of the latex, or by theaction of supplemental catalysts of the same type. Polymerizationconditions are continued until the amount of the added monomeric mixturewhich has graft copolymerized upon the latex amounts to from 10% to 80%of the entire resultant graft copolymer. The resultant latex is eithercoagulated at once to recover the graft copolymer for mill-mixing withthe other constituents, or the latex is used for blending with the otheringredients in latex form.

The vinyl chloride resin This may be a homopolyrner of vinyl chloride,or a copolymer thereof with minor proportions of other ethylenicallyunsaturated compounds copolymerized therewith. In a preferred form ofthe invention, the vinyl chloride resin is a simple homopolymer of vinylchloride, since the hardest and most rigid compositions are obtainablewith the homopolymcrs of vinyl chloride; however, the resin may containup to 20% of other unsaturated compounds copolymerizable with vinylchloride without detracting from the essential nature of the vinylchloride resin. Conversely stated, the resins should have at least 80%of vinyl chloride copolymerized therein. Suitable unsaturated compoundsinclude, for instance, vinylidene chloride, vinylidene bromide,vinylidene fluorochloride, and the like; unsaturated hydrocarbons suchas ethylene. propylene, isobutene and the like; allyl compounds such asallyl acetate, allyl chloride, aliyl ethyl ether and the like; andconjugated and cross-conjugated ethylenically unsaturated compounds suchas butadiene, isoprenc, chloroprene, 2,3-dimethylbutadiene 1,3,piperylene, divinyl ketone and the like. For a fairly complete list ofmaterials known to polymerize with vinyl chloride, reference may be hadto Krczil: Kurzes Handbuch Der PolymerisationsTechnik-l1 MehrstoffPolymerization Edward Bros. Inc., 1945, pp. 735-747, the items underVinyl chlorid. As a rough rule, the criterion of a practical comonomerfor use with vinyl chloride, to produce copolymers containing 80% ormore of vinyl chloride is that, on a mole percentage basis, an initialcharge of 96% vinyl chloride, balance comonomer, shall yield an initialcopolymer containing (a) at least 90% vinyl chloride, and (b) not morethan 99% vinyl chloride. On this basis, satisfactory comonomers for usewith vinyl chloride will be those having Q2 and e2 values, as describedin J. Polymer Science 2:101, correlated as follows, assuming for vinylchloride Qvinyl chloride d vinyl chloride Instead of the singleunsaturated comonomers of the types above indicated, mixtures of suchcomonomers may enter into the copolymers, it being understood that thetotal quantity thereof shall be small enough (i. e., not over 20% basedon the weight of the copolymer) that the essential character of thepolyvinyl chloride chain is retained.

Compounding the compositions of this invention The proportions of theessential vinyl chloride resin and graft copolymer, and the optionalproportions of pigment and compounding ingredients have been set outhereinabove. The greatest advantage of this invention is obtained in thecase of rigid, substantially unplasticized vinyl resin compositions, andfor this purpose any cornpounding materials capable of dissolving in thevinyl chloride resin and of plasticizing it should be kept at relativelylow levels, say 10% or less, based on the weight of vinyl chloride resinin the compositions.

Referring to the mode of compounding the materials of this invention,one convenient method is to thoroughly mix together latices containingthe vinyl chloride resin and graft copolymer, and thereafter to add acoagulating agent to cause all the materials to be simultaneouslycoprecipitated from the mixed latex. This method has the advantage ofready and accurate measurement, a some what more thorough and reliableblending, and a saving in power expenditure over mill mixing. Thealternative is, of course, to blend solid components by means of a rollmill, banbury mill or the like. No great difference in propertiesbetween compositions prepared by the two methods has been noted.

Compositions according to this invention are used in any of theapplications where vinyl chloride resins have heretofore been employed,and in any given formulation will exhibit properties equal or superiorto vinyl chloride resins in all respects. A preferred aspect of theinvention is concerned with unplasticized rigid vinyl chloride resinformulations in which the vinyl chloride resin is essentially a simplepolyvinyl chloride containing little or no comonorners copolymerizedtherein, and which contain little or no (say less than 10%) of materialswhich are soluble in the polyvinyl chloride and which would plasticizethe same. Such compositions have properties substantially identical inmodulus, hardness and heatdistortion temperatures with conventionalrigid polyvinyl chloride formulations; in addition to this, thecompositions of this invention have sharply superior impact strengths ascompared with corresponding conventional rigid vinyl chlorideformulations. The compositions of this invention are therefore vastlysuperior replacements for rigid vinyl resin in the applications in whichthe latter have had such remarkable success, viz., in piping, fittings,fume ductwork, vessels and vessel linings, pump and fan vanes andimpellers, treatment racks and the like in chemical and processindustries.

With the foregoing general discussion in mind, there are given herewithdetailed examples of the practice of this invention. All parts given areby weight.

A series of substrates was prepared for graft copolymerization inaccordance with Table III, using the ingredients set forth in Table IIin the proportions indicated in columns L, M, N and O in the respectivepreparations. In each case the selected ingredients were charged into apolymerization vessel, the free space of which was then purged withbutadiene vapor. The charge was polymerized at 50 C. for 16 hours underautogenous pressure, resulting in conversion of approximately 98% of themonomeric material to polymeric form. At the end of the polymerizationperiod the as-yet-unpolymerized monomers were vented, and the resultantlatex, containing approximately 33% of polymeric material, cooled to 25C. The latices derived from the charges containing 100, 90, and 75 partsof butadiene are hereinafter designated respectively as latices L, M, Nand O.

2 Per Table III.

A series of graft copolymers was prepared in accordance with theforegoing recipe, using as the latex in each case on of the latices L, Mor O prepared as described above under A. Preparation of Substrates.Likewise, the styrene/acrylonitrile ratio was varied in certain of thegraft copolymers. In each case the selected ingredients were chargedinto a polymerization vessel, the free space of which was then purgedwith nitrogen. The vessel was then sealed, and polymerization carriedout with agitation at 50 C. for 4 hours, at the end of which time all ofthe styrene and acrylonitrile had become polymerized by graftcopolymerization upon the butadiene polymer (or copolymer) in the latex.The charge was then cooled to 25 C. and stabilized by the addition of 4parts of a heptylated diphenyl amine (Agerite Stalite, a product of theR. T. Vanderbilt Co.) and 4 parts of dimethyl ammonium dimethyldithiocarbamate.

The resultant latex was coagulated by slowly pouring 3 volumes of thelatex into 5 volumes of a 1% aqueous calcium chloride solution, withvigorous stirring. The coagulated graft copolymer was dewatered byfiltration, washed on the filter with water and dried in an oven at 60C.

C. Compounding with vinyl chloride resin Parts Vinyl chloride resin("Exon 402-A, a polyvinyl chloride manufactured by The Firestone Tire &Rubber Co.) 90, 85, 80, 75, 65 or 50 (per Table III) Graft copolymer(prepared as above described; containing a substrate of purepolybutadiene; 90% butadiene/ acrylonitrile; or 75% butadiene/%acrylonitrile as indicated in Table III)- 10, 15, 20, 25, or (per posesof comparison, there was also prepared a composition comprising thevinyl chloride resin without any graft copolymer.

Laminates were prepared from this It will be seen that the vinylchloride (item No. 23), but coupled with these excellent properties theyhave impact strengths far exceeding that of the unmixed polyvinylchloride. be noted that these excellent impact properties persist Itwill T bl [11) even at very low temperatures, note the values givenCadmium lauryl mercaptide 2 la under 0 C. in the table.

TABLE III Graft Goplymer Used Notched Izod Impact Weight Strength([tlhs/in. notch) Ratio Vinyl Hardness Modulus Heat Dls- Weight ofChloride (Rockwell, (Pounds tortion It Styrene in Resin/Graft R-Scale)per square 'Iernp ra- N Substrate Grafted Copolymer LElCh) ture C.) AtAt at Monomers, 25 0. 0 0. 0.

Percent 90/10 107 300,000 71 24. 4 0.8 1 85/15 105 340, 000 71 21.0 D. 62 "o" 75% Butadlene)--. 78 30/20 102 250, 000 71 25. a 1. r 0. s a 75/2594 250, 000 68 23. 6 14. 4 0. 6 4 /35 89 267, 000 05. 5 26. 2 15. 2 0. 85 90/10 103 340, 0 18. 5 l. 0 6 85/15 102 33g, 70 l; 1. 4 7

2 1 (90% Bumdiene) 78 ii? $91003 71 9. 5 iii 8 66/35 88 216, 000 71 10.1 12. 5 9. 3 1[) 50/50 70 188, 000 70 10. 8 9. 6 S. 8 11 130/10 105 376,000 72 17. 6 1. 2 0.8 12 85/15 98 307, 000 72 16. T 16. 7 4. i5 13 7880/20 93 290, 000 71 10. 5 16. 7 14.3 14 /25 88 269,000 72 15.7 16.315.4 15 65/35 75 66 14. 6 12. 6 NA 16 14" (100% Butadiene). 50/50 47168, 000 68 8. 8 9. 2 7. 8 17 85415 103 320, (100 72 16. 4 9. (l l. 6 18/20 98 307, 000 72 17.3 17.4 6. 5 19 68 7.5/25 94 .000 71 10.9 17. 614.1 20 05/35 255, 000 71 10. 2 15. i] 15. 4 21 50/50 62 202. 000 69 12.9 11.2 11. 3 22 /0 114 .370, 000 73 0.5 23

A series of compositions was made up in accordance with the foregoingschedule, using various of the graft ccpolymers prepared as describedhereinabove with vari- 7 ous proprotions of the vinyl chloride resin. Ineach case the selected graft copolymer together with the selected amountof the vinyl chloride resin were blended together on a roll mill heatedto 320 F. The resin was handed first on the mill and thereafter thegraft copolymer and cadmium mercaptide were added and milling continuedwith frequent cutting. At the end of 3 minutes the stock was sheeted offthe mill at a thickness of approximately 0.02 inch.

Six-ply laminates were prepared from the sheets removed from the mill asabove described. In each case the sheets, cut into squares six inches ona side, were stacked in a flat platen press and laminated in a cycleconsisting of (A) a three-minute preheat with pressplatens at 180 C.,(B) a three-minute application of a total load of 840 tons withpressplatcns still at l80 C.. (C) a three-minute cooling cycle underpressure with cold Water circulation in the platens, and (D) removalfrom the press. Set forth herewith in Table 111 are the compositionsprepared and the physical properties of the laminates. It will be seenthat all of the products of this invention (items l22) are characterizedby high values of hardness, modulus and heat distortion temperatures,coupled with high impact strength both at room temperature and atsubnormal temperatures. For pur- EXAMPLE II.-STYRENE-ACRYLONITRILE-ISOBUTYLENE MIXTURE GRAFT A. Preparation of graft copolymer A series ofgraft copolymers was made up in accordance with the above recipe, usingin each case the substrate latex, styrene, acrylonitrile and isobutyleneas indicated in Table IV. chargcd into a polymerization vessel, the freespace of which was then purged with nitrogen.

in each case the selected ingredients were Polymerization "was carriedout with agitation at 50 C. for 4 hours, at the end of which timesubstantially all of the styrene, acrylonitrile and isobutylene hadbecome polymerized. Any small traces of unpolymerized isobutylene werethen 5 vented, and the resultant latex cooled to 25 C. and

stabilized by the addition of 4 parts of a heptylated di- B. Preparationof graft copolymer phenyi amine (Agerite Stalite," a product of the R.T. Parts Vanderbilt Company) and 4 1 arts of dimethyl ammoniumButadiene-styrene latex (Latex P, prepared as just dirncthyldithiocarbamate. described) 1 300 The resultant latex was coagulated byslowly pouring Styrene 78 3 volumes of the latex into 5 volumes of a 1%aqueous crylomtnle 22 calcium chioride solution with vigorous stirring.The Potassium persultate 0.4 congulated graft copolymer was dewatcred byfiltration, Dodecyl mercaptan 0.4 washed on the filter with water, anddried in an oven Water 200' at 60 C. Provides 100 parts or rubber.

B. Compounding with vinyl chloride resin The above ingredients weresubjected to poiymerizatiom. Parts and the graft copolymers recoveredand dried as de-- scribed in Exam 1 IB. P Vinyl chloride resin (Exon402-A, a polyvinyl 1, P e reparation of Graft Copoly chloridemanufactured by The Firestone Tire & Rubber 1 80 95 C. Compounding withvmyl chloride resm Graft copolyrner (prepared as above described) 1 520Vinyl chloride resin (Emu a poly Cadmlum lauryl mercapnde 2 vinylchloride, manufactured by The Part Pe1- Table IV. 90 Firestone Tire andRubber Co.) 1 90: Q1 80 A series of compositions was made up inaccordance with Graft Fopolymer as 1 1 to: the foregoing schedule, usingthe resin and graft copoly- Cadmium lam'yl mercapude mer in variousproportions as set forth in Table IV here- 1 Per Table V. inbelow. Ineach case the ingredients, in the selected proportions, were blended andformed into iaminated 5 TWO cfmlposltlons were mad? In aCcOrdanCe iththe sheets as described in Example 1 above Set forth in foregoingschedule, and fabricated into six-ply laminates. Table IV are theproperties of the specimens prepared. as described above in Example C.Compounding with;

TABLE IV Substrate Latex Grafted Monomers Properties (parts used inrecipe) Weight Ratio of Resin to Modulus Heat Notched Izod ImpactStrength Item Percent Graft Hardness (Pounds Distor- (Ft.-Lbs./In.Notch) at- N 0. Designs.- Bntadiene Styrene Acrylo- Isobu- Oopolymer(Rockwell per sq. tion tion in rubber nitrile tyiene R-scale) inch)Temp,

"0. C. 10C. 0C. -20C 00/10 105 370. 000 72 17.0 1.2 0.3 1 78 22 0 85/1500 307, 000 72 6.7 10.7 4.0 2 L 100 /20 03 200.000 71 10.5 10.7 11.3 36B 0 15 103 320. 000 72 16.4 0.0 1.0 4 30/20 0a 301, 72 17.3 1?.4 0.5 s.00 at 12-2 2* 1 i N 80 n 39 10 85/15 07 275, 000 21.0 a 00/20 34202.000 05 20 0 L 100 0 65 35 00/10 102 289. 000 0. 4 10 o 20 /10 107372,000 0.6 11 M 00 20/80 07 258, 000 71 0. 7 12 0 65 35 00/10 114 317,000 74 2. 4 13 EXAMPLE III.-BUTADIENE-S'I'YRENE 55 Vinyl Chloride Resin.Tabulated herewith are the:

SUBSTRATE properties of the products.

A. Preparation of substrate TABLE V 7 Parts Bntadiene 90 Properties 6Otytene 10 Its/eight t'oot Ha 1- 1111 Hit Nt-h.il. I i. Potesmm its...as. that: S.;*..2,:1 atae,tt Dodecyi mCI'CElpmii 0.05 O Grlnit(Roriihper Ttion Notch) nta 'n1 Water 200 i w 23 gg 3 3 5 0 0. 20(}. Theabove ingredients were charged into a polymerization vessel, the freespace of which was then purged with butag0/1Q 103 330,000 75 112 U 0.5diene vapor. The vessel was then sealed, and the poly- 103 209,000 7615.2 13.9 1.3 merization carried out with agitation at 50 C. for l-6hours, at the end of wh' h tim he in nom e 70 EXAMPLE IV.ALPHA-METHYLSTYRENE- uents were substantially completely polymerized. TheACRYLONITRILE GRAF as-yet-u11polymerized monomers were then vented, andT the resultant latex, containing approximately 33% of The procedure ofExample III was extractly repeated, a copolymer of 90% butadiene, 10%styrene, was cooled except that the 78 parts of styrene were replaced by60 to 25 C. This latex will hereinafter be designated parts ofalpha-methyl styrene and the 22 parts of acryloas Latex P. 75 nitrilewere replaced by 40 parts of acrylonitrile in the recipe under B.Preparation of Graft copolymer." Following are the results obtained.

From the foregoing general description and detailed specific examples,it will be evident that this invention provides novel resinouscompositions having all of the desirable properties of unplasticizedpolyvinyl chloride compositions, coupled with excellent toughness andimpact strength at both normal and low temperatures. Polyvinyl chloridecompositions heretofore prepared are well known to be seriouslydeficient in these last particulars. The compositions of this inventionare therefore far superior to simple polyvinyl chloride compositions inthose applications in which polyvinyl chloride has been successful, andmoreover are applicable in fields in which the polyvinyl chloride cannotbe used, i. e., in situations subject to shock and impact loads.

What is claimed is:

1. A composition comprising Percent (A) A vinyl chloride resin 1 50-95blended with (B) A graft copolymer of a styrene-acrylonitrile-typemixture upon a diene rubber 1 5-50 t 1 Based on the total weight of (A)plus (B) in the composisaid vinyl chloride resin (A) being selected fromthe group consisting of homopolymers of vinyl chloride and copolymersthereof with other unsaturated compounds copolymerizable therewith andsaid copolymers contain ing at least 80% of vinyl chloride copolymerizedtherein, and said graft copolymer (B) being a graft copolymer producedby graft polymerizing a charge of Percent (C) Astyrene-acrylonitrile-type mixture of monomers 1 l080 upon (D) A dienerubber 90-20 1 Based on the weight of (C) plus (D).

said styrene-acrylonitrile-type mixture (C) being selected from thegroup of compositions consisting of those within the system styrene,alpha-methyl styrene, acrylonitrile, methacrylonitriie, isobutylene, theproportions of these compounds lying within a quadrilateral PQRS on atrilinear chart whose corners represent respectively (E) the sum, of thepercentages of styrene and alpha-methyl styrene, (F) the sum of thepercentages of acrylonitrile and methacrylonitrile and (G) isobutylene,the vertices of said quadrilateral having the following coordinates onsaid chart 12 (H) A compound selected from the group Percent consistingof butadiene, isoprene and mixtures thereof 60-400 (I) Acrylonitrile,alpha-methyl acrylonitrile,

styrene, alpha-methyl styrene and mixtures thereof Up to 40 (1) Othernon-cross-linking monomers copolymerizable with butadiene and isopreneUp to 10 ('K) Other cross-linking monomers copolymcrizablc withbutadiene and isoprene Up to 3 Based on the weight of (H) plus (1) plus(J) plus (K).

2. A composition comprising Percent (A) Polyvinyl chloride 5095 blendedwith (B) A graft copolymer of a styrene acrylonitrile-type mixture upona diene rubber 1 5-50 Based on the total weight of (A) plus (B) in thecomposition.

said graft copolymer (B) being a graft copolymer produced by graftpolymerizing a charge of (C) A styrene-acrylonitrile-type mixture ofmonomers l() upon (D) A diene rubber -20 1 Based on the weight of (C)plus (D).

said styrene-acrylonitrile-type mixture (C) being selected from thegroup of compositions consisting of those within the system styrene,alpha-methyl styrene, acrylonitrile, methacrylonitrile, isobutylene, theproportions of these compounds lying Within a quadrilateral PQRS on atrilinear chart Whose corners represent respectively (E) the sum of thepercentages of styrene and alpha-methyl styrene, (F) the sum of thepercentages of acryionitrile and methacrylonitrile and (G) isobutylene,the vertices of said quadrilateral having the following coordinates onsaid chart Coordinates E F (.1 Vertex of Quadrilateral Sum of Sty- Sumof Acryrene plus lonitrile plus Alplia- Alpha lsobutylcne methyl methylacry- Styrene lonitrile 0 s5 15 50 50 0 90 10 0 0 s5 s5 and said dienerubber (D) having polymerized therein Percent (H) A compound selectedfrom the group consisting of butadiene, isoprene and mixtures thereof60400 (I) Acrylonitrile, alpha-methyl acrylonitrile,

styrene, alpha-methyl styrene and mixtures thereof 1 Up to 40 (1) Othernon'cross-linking monomers copolymerizable with butadiene and isopreneUp to 10 (K) Other cross-linking monomers copolymerizable with butadieneand isoprene Up to 3 Buscd on the Weight of (H) plus (1) plus (J) plus(K). 3. A composition comprising Percent (A) A vinyl chloride resin 15095 blended with (B) A graft copolymer of a styrene-acrylonitrile-typemixture upon a diene rubber 1 5-50 it; Based on the total weight of (A)plus (B) in the compos on.

said vinyl chloride resin (A) being selected from the group consistingof homopolymers of vinyl chloride and copolymers thereof with otherunsaturated compounds copolymerizable therewith and said copolymerscontaining at least 80% of vinyl chloride copolyrnerized therein, andsaid graft copolymer (B) being a graft copolymer produced by graftpolymerizing a charge of Percent (C) A styrene-acrylonitrile-typemixture of monomers 1 40-80 upon (D) A diene rubber 90-20 1 Based on theweight of (C) plus (D).

said styrene-acrylonitrile-type mixture (C) being selected from thegroup of compositions consisting of those Within the system styrene,alpha-methyl styrene, acrylonitrile, methacrylonitrile, isobutylene, theproportions of these compounds lying within a quadrilateral PQRS on atrilinear chart whose corners represent respectively (B) the sum of thepercentages of styrene and alpha-methyl styrene, (F) the sum of thepercentages of acrylonitrile and methacrylonitrile and (G) isobutyiene,the vertices of said quadrilateral having the following coordinates onsaid chart Coordinates E F G Vertex of Quadrilatcrnl Sum of Sty- Sum ofAcryreneplus lonltrlle plus Alpha- Alpha Isobutylene methyl methyl acry-Styrene lonitrile 85 15 50 50 O 9O 10 O t) 65 35 and said diene rubber(D) having polymerized therein said composition containing not over 10%,based on the Weight of vinyl chloride resin therein, of compoundingingredients soluble in the vinyl chloride resin.

1 Gil-100 4. A composition comprising Percent (A) Polyvinyl chloride 150-95 blended with (B) A graft copolymer of a styrene-acrylonitrile-typemixture upon a diene rubber 1 5 3 said graft copolymer (B) being a graftcopolymer produced by graft polymerizing a charge of Percent (C) Astyrene-acrylonitrile-type mixture of monomers 2 -30 upon (D) A dienerubber 90-20 t Based on the total weight of (A) plus (B) in the compo-0!]. 3 Based on the weight of (C) plus (D).

said styrene-acrylonitriletype mixture (C) being selected from the groupof compositions consisting of those within the system styrene,alpha-methyl styrene, acrylonitrile, methacrylonitrile, isobutylene, theproportions of these compounds lying within a quadrilateral PQRS on atri- 14 linear chart whose corners represent respectively (B) the sum ofthe percentages of styrene and alpha-methyl styrene, (F) the sum of thepercentages of acrylonitrile and methacrylonitrile and (G) isobutylene,the verticcs of said quadrilateral having the following coordinates onsaid chart Coordinates E F G Vertex of quadrilateral Sum of Sty- Sum ofAcryrene plus ionltrile plus Alpha- Alphn- Isobutylcno methyl methylacry- Btyrene lonitrile and said diene rubber (D) having polymerizedtherein Percent (H) A compound selected from the, group consisting ofbutadiene, isoprene and mixtures thereof 1 60l00 (I) Acrylonitrile,alpha-methyl acrylonitrile, styrene, alpha-methyl styrene and mixturesthereof 1 up to 40 (J) Other non-cross-linking monomers copolymerizablewith butadiene and isoprene 1 up to 10 (K) Other cross-linking monomerscopolyrnerizable with butadiene and isoprene 1 up to 3 Based on theweight of (H) plus (I) plus (J) plus (K).

said composition containing not over 10%, based on the weight ofpolyvinyl chloride, of compounding ingredients soluble in the polyvinylchloride.

5. A composition comprising Percent (A) Polyvinyl chloride 1 9O blendedwith (B) A graft copolymer of a styrene-acrylonitriletype mixture upon adiene rubber 1 10 said graph copolymer (B) being a graft copolymerproduced by graft polymerizing a charge of (C) Astyrene-acrylonitrile-type mixture of monomers 2 10-80 upon (D) A dienerubber it iBased on the total weight of (A) plus (B) in the compo S 011.

Based on the weight of (C) plus (D).

said styrene-acrylonitrile-type mixture (C) being selected from thegroup of compositions consisting of those within the system styrene,alpha-methyl styrene, acrylonitrile, methacrylonitrile, isobutylene, theproportions of these compounds lying within a quadrilateral PQRS on atrilinear chart Whose corners represent respectively (E) i the sum ofthe percentages of styrene and alpha-methyl styrene, (F) the sum of thepercentages of acrylonitrile and methacrylonitrile and (G) isobutylene,the vertices of said quadrilateral having the following coordinates on.said chart Coordinates e E F G Vertex o! quadrilateral Sum of Sty- Sumof Acryrcne plus lonitrile plus Alphu- Alpha Isobutylene methyl methylacry- Styrene lonitrlle 0 15 50 50 G 1G 0 D 65 35 and said diene rubber(D) having polymerized therein Percent (H) A compound selected from thegroup consisting of butadiene, isoprene and mixtures thereof 1 60100 (1)Acrylonitrile, alpha-methyl acrylonitrile,

styrene, alpha-methyl styrene and mixtures thereof 1 Up to 40 (J) Othernon-cross-linking monomers copolymerizable with butadiene and isoprene 1Up to 10 (K) Other cross-linking monomers copolymerizable with butadieneand isoprene 1 Up to 3 Based on the weight of (H) plus (I) plus (3')plus (K). said composition containing not over 10%, based on the weightof polyvinyl chloride, of compounding ingredients soluble in thepolyvinyl chloride.

6. A composition comprising Percent (A) A vinyl chloride resin 1 50-95blended with (B) A graft copolymer of a styrene-acrylonitriletypemixture upon a diene rubber 1 5-50 t Based on the total weight of (A)plus (B) in the compo- 511011,

said vinyl chloride resin (A) being selected from the group consistingof homopolymers of vinyl chloride and copolymers thereof with otherunsaturated compounds copolymerizable therewith and said copolymerscontaining at least 80% of vinyl chloride copolymerized therein, andsaid graft copolymer (B) being a graft copolymer produced by graftpolymerizing a charge of Percent (C) A styrene-acryloni[rile-typemixture of monomers 1 -80 upon (D) Polybutadiene 9020 1 Based on theWeight of (C) plus (D).

said styrene-acrylonitrile-type mixture (C) being selectcd from thegroup of compositions consisting of those within the system styrene,alpha-methyl styrene, acrylonitrile, methacrylonitrile, isobutylene, theproportions of these compounds lying within a quadrilateral PQRS on atrilinear chart whose corners represent respectively (E) the sum of thepercentages of styrene and alpha-methyl styrene, (F) the sum of thepercentages of acrylonitrile and methacrylonitrile and (G) isobutylene,the vertices of said quadrilateral having the following coordinates onsaid chart Coordinates E F G Vertex of Quadn'lateral Sum of Sty- Sum ofAcryrene plus lonitrlle plus Alpha- Alpha- Isobutylene methyl methylacry- Styrene lonitrile 7. A composition comprising Percent (A)Polyvinyl chloride -95 blended with (B) A graft copolymer of astyrene-acrylonitriletype mixture upon polybutadiene 1 5-50 said graftcopolymer (B) being a graft copolymer produced by graft polymerizing acharge of Percent (C) A styrene-acrylonitriletype mixture of monomers 210-80 upon (D) Polybutadiene 90-20 {Based on the total weight of (A)plus (B) in the compos1 mu.

1 Based on the weight of (C) plus (D).

said styrene-acrylonitrile-type mixture (C) being selected from thegroup of compositions consisting of those Within the system styrene,alpha-methyl styrene, acrylonitrile, methacrylonitrile, isobutylene, theproportions of these compounds lying Within a quadrilateral PQRS on atrilinear chart whose corners represent respectively (B) the sum of thepercentages of styrene and alpha-methyl styrene, (F) the sum of thepercentages of acrylonitrile and alphamethyl acrylonitrile, and (G)isobutylene, the vertices of said quadrilateral having the followingeoordinates on said chart.

Coordinates E F G Vertex 0t Quadrilateral Sum of Sty- Sum of Acry reneplus loultrlle plus Alpha- Alpha- Isobutylene methyl methyl acry-Styrene lonitrile 8. A composition comprising Percent (A) Polyvinylchloride 1 blended with (B) A graft copolymer of astyrene-acrylonitrile-type mixture upon polybutadiene 1 10 said graftcopolymer (B) being a graft copolymer produced by graft polymerizing acharge of (C) A styrene-acrylonitrile-type mixture of monomers 10-80upon (D) Polybutadiene t Based on the total weight of (A) plus (B) inthe compoion. 2 Based on the weight of (C) plus (D).

said styrene-acrylonitrile-type mixture (C) being selected from thegroup of compositions consisting of those within the system styrene,alpha-methyl styrene, acrylonitrile, methacrylonitrile, isobutylene, theproportions of these compounds lying Within a quadrilateral PQRS on atrilinear chart whose corners represent respectively (E) the sum of thepercentages of styrene and alpha-methyl styrene, (F) the sum of thepercentages of acrylonitrile and methacrylonitrile and (G) isobutylene,the vertices of said quadrilateral having the following coordinates onsaid chart i Based on the total weight of (A) plus (B) in the compostion.

17 said vinyl chloride resin (A) being selected from the groupconsisting of homopolymers of vinyl chloride and copolymers thereof withother unsaturated compounds copolymerizable therewith and saidcopolymers containing at least 80% of vinyl chloride copolymerizedtherein, and said graft copolymer (B) being a graft copolymer producedby graft polymerizing a charge of lercent (C) Astyrene-acrylonitrile-type mixture of monomers W- 7 upon (D) A rubberycopolymer of 90% butadiene, 10% acrylonitrile, based on the weight ofthe rubbery eopolyrner 90-40 1 Based on the weight of (C) plus (D).

said styrene-acrylonitrile type mixture (C) being selected from thegroup of compositions consisting of those within the system styrene,alpha-methyl styrene, acrylonitrile, methacrylonitrile, isobutylene, theproportions of these compounds lying within a quadrilateral PQRSVnn atrilinear chart Whose corners represent respectively (B) the sum of thepercentages of styrene and alpha methyl styrenc, (F) the sum of thepercentages of acrylonitrile and methacrylonitrile and (G) iso'outylene,the vertices of said quadrilateral having the following coordinates onsaid chart Coordinates E F G Vertex o! Quadrilateral Sum o! Sty- Sum ofAcryrene plus lonltrile plus Alpha- Alpha- Isobutylene methyl methylacry- Styrene lonitrile 85 15 Si) 60 0 9o 0 0 65 35 10. A compositioncomprising Percent (A) Polyvinyl chloride 1 50-95 blended with (B) Agraft copolymer of a styrene-acrylonitriletype mixture upon a rubberycopolymer of butadiene and acrylonitrile 5 5-50 said graft copolymer (B)being a graft copolymer produced by graft polymerizing a charge of (C) Astyrene-acryionitrile-type mixture of monomers '-1080 upon (D) A rubberycopolymer of 90% butadiene, 16% acrylonitrile, based on the weight ofthe rubbery copolymer 90-20 it: Based on the total Weight of (A) plus(B) in the compos on.

Based on the weight oi. (C) plus (D).

said styrene-acrylonitrilc-type mixture (C) being selected from thegroup of compositions consisting of those within the system styrene,alpha-methyl styrene, acrylonitrile, methacrylonitrile, isobutylene, theproportions of these compounds lying within a quadrilateral PQRS on atrilinear chart Whose corners represent respectively (E) the sum of thepercentages of styrene and alpha-methyl styrene, (F) the sum of thepercentages of acrylonitrile and methacrylonitrile and (G) isobutylene,the vertices of said quadrilateral having the following coordinates onsaid chart said graft coploymer (B) being a graft copolymer produced bygraft polymerizing a charge of Percent (C) A styrene-acrylonitriletypemixture of monomers 10-80 upon (D) A rubbery copolymer of 90% butadiene,10% acrylonitrile, based on the weight of the rubbery copolymer 3 90-205 Based on tne total weight or (A) plus (B) in the compo- DH. Based onthe weight of (C) plus (13).

said styrene-acrylonitrile-type mixture (C) being selected from thegroup of compositions consisting of those within the system styrene,alpha-methyl styrene, acrylouitrile, methacrylonitrile, isobutylene, theproportions of these compounds lying Within a quadrilateral PQRS on atrilinear chart whose corners represent respectively (E) the sum of thepercentages of styrene and alpha-methyl styrene, (F) the sum of thepercentages of acrylonitrile and methacrylonitrile and (G) isobutylene,the vertices of said quadrilateral having the following coordinates onsaid chart Coordinates E F G Vertex or quadrllateral Sum of Sty- Sum ofAcryrene lus lonltrlle plus Alp ia- Alphn- Isobutyleue methyl methylacry- Styrcue lonitrtle 0 s5 15 no so 0 so 10 0 0 65 35 12. Acomposition comprising Percent (A) A vinyl chloride resin 1 50-95blended with (B) A graft copolymer of a styrene-acrylonitriletypemixture upon a rubbery copolymer of butadiene and acrylonitrile l 5-50Based on the total weight or (A) plus (B) in the compo S 10D.

said vinyl chloride resin (A) being selected from the group consistingof homopolymers of vinyl chloride and copolymers thereof with otherunsaturated compounds copolymerizable therewith and said copolymerscontaining at least of vinyl chloride copolymerized therein, and saidgraft copolymer (B) being a graft polymer produced by graft polymerizinga charge of Percent (C) A styrene-acrylonitrile-type mixture of monomers10-80 upon (D) A rubbery copolymer of 75% butadiene,

25% acrylonitrile, based on the weight of said rubbery copolymer 1 90-201 Based on the weight of plus (D). said styrene-aerylonitrile-typemixture (C) being selected from the group of compositions consisting ofthose within the system styrene, alpha-methyl styrene, acrylonitrile,methacrylonitrile, isobutylene, the proportions of these compounds lyingwithin a quadrilateral PQRS on a trilinear chart whose corners representrespectively (E) the sum of the percentages of styrene and alpha-methylstyrene, (F) the sum of the percentages of acrylonitrile andmethacrylonitrile, and (G) isobutylene, the vertices of saidquadrilateral having the following coordinates on said chart said graftcopolymer (B) being a graft copolymer pro duced by graft polymerizing acharge of (C) A styrene-acrylonitrile-type mixture of monomers 2 10-80upon (D) A rubbery copolymer of 75% butadiene, 25% acrylonitrile, basedon the weight of said rubbery copolymer 90-20 fised on the total weightof (A) plus (B) in the composition.

9 Based on the weight of (C) plus (D).

4 said styrene-acrylonitrile-type mixture (C) being selected cgordjnatggfrom the group of compositions consisting of those within the systemstyrene, alpha-methyl styrene, acrylonitrile, E F G methacrylonitrile,isobutylcne, the proportions of these Vertex flfQufldrilatml Sum Gist?Sum of Act? compounds lying within a quadrilateral PQRS on a rene luslonltl-ile plus trlllnear chart whose corners represent respectlvely (E)3 Alpha Imbutylene the sum of the percentages of styrene andalpha-methyl yl methyl acry- Styrene lonltrile styrene, (F) the sum ofthe percentages of acrylonltrlle and methacrylonitrile and (G)isobutylene, the vertices of 0 a5 15 said quadrilateral having thefollowing coordinates on 33 s 8 said chart 13. A composition comprisingCoordinates Percent (A) Polyvinyl chloride aws 35 E F G blended withVertex of quadrilateral (B) A graft copolymer of astyrene-acrylonitrile, g g f g f'f gg gg' type mixture upon a rubberycopolymer of buta- Alpha- Alpha- Isobutyleue diene and acrylonitrile 15-50 40 5,251 323:3 35 said graft copolymer (B) being a graft copolymerproduced by graft polymerizing a charge of 3 2g 3 Percent 90 10 0 (C) Astyrene-acrylonitrile-type mixture of 0 65 35 monomers 10-80 upon (D) Arubbery copolymer of 75% butadiene, 15. A composition comprising 25%acrylonitrile, based on the weight of said Percent rubbery copolymer90--20 (A) Polyvinyl chloride 90 Based on the total weight of (A) plus(B) in the compoblended Wlth on. (B) A graft copolymer of astyrene-acrylonltrlle Based on the s of p mixture upon polybutadiene 110 said styrcne-acrylonitrile-type mixture (C) being selected from thegroup of compositions consisting of those within sald graft copolymer(B) bemg a graft copolymer of the system styrene, alpha-methyl styrene,acrylonitrile, (C) A styrene-acrylonitrile mixture 50 methacrylonitrile,isobutylene, the proportions of these upon compounds lying within aquadrilateral PQRS on a tri (D) Polybutadiene 50 linear chart whosecorners represent respectively (B) the Sum of the percmtages of Styreneand alpha methyl st? and said styrene acrylonltrlle mixture (C)comprlslng rene, (F) the sum of the percentages of acrylonitrile andStyrene 3 78 methacrylonitrile and (G) isobutylene, the vertices of saidand quadrilateral having the following coordinates on saidAfl'ylonitl'fle 322 chart 1; Based on the total weight of (A) plus (B)in the composea assassin: a: as: 12;.- E F G 16. A compositioncomprising Vertex of quadrilateral S is, Sum of A" Percent gg g lemmeP01rvmy1 ch10r1de 90 Alp a- Alpha- Isobutylene blended with g methyl?-(B) A graft copolymer of a styrene-acrylonitrileyrene lonltrllolsobutylene mlxture upon a rubbery copolymer of 0 85 15 butadiene andacrylonitrile 10 50 50 0 Based on the total weight of (A) plus (B) inthe compog 2 g tlon.

said graft copolymer (B) being a graft copolymer of (C) Astyrene-acrylonitrile-isobutylene mixture 2 40 upon (D) A rubberybutadiene-acrylonitrile copolymer 3 60 saidstyrene-acrylonitrile-isobutylene mixture (C) comprising (E) Styrene 318 (F) Acrylonitrile 3 65 (G) Isobutylene 17 and saidbutadiene-acrylonitrile copolymer (D) comprising a copolymer of (H)Butadiene 80 and (I) Acrylonitrile 20 3 Based on the weight of (C) plus(Di Based on the Wei ht of E) lusf plus (G).

4 Based on the welg t of( p us 17. A composition comprising Percent (A)Polyvinyl chloride 1 80 blended with (B) A graft copolymer of analpha-methyl styreneacrylonitrile mixture upon a rubberybutadienestyrene copolymer 20 said graft copolymer (B) being a graftcopolymer of (C) A mixture of alpha-methyl styrene and acrylonitrile 950 upon (D) A rubbery butadiene-styrene copolymer 50 said mixture (C) ofalpha-methyl styrene and acrylonitrile comprising (E) Alpha-methylstyrene 3 60 and (F) Acrylonitrile 40 and said butadiene-styrenecopolymer (D) comprising a copolymer of (H) Butadiene 90 and (I) Styrene*10 {Based on the total weight of (A) plus (B) in the compo 3 Based onthe weight of plus (D).

3 Based on the weight of E) plus (F).

* Based on the weight of (H) plus (I).

18. A composition comprising Percent (A) Polyvinyl chloride 1 90 blendedwith (B) A graft copolymer of a styrene-acrylonitrile mixture upon arubbery copolymer of butadiene and acrylonitnle 1 Based on the totalweight of (A) plus (B) in the compos ion.

Based on the weight of (C) plus (D 3 Based on the weight of 1!] plus (FBased on the weight of plus (I 19. A composition comprising Percent(A)Polyvinyl chloride 1 90 blended with (B) A graft copolymer of astyrene-acrylonitrile mixture upon a rubbery copolymer of butadiene andstyrene 1 10 said graft copolymer (B) being a graft copolymer of (C) Astyrene-acrylonitrile mixture 2 upon (D) A rubbery copolymer ofbutadiene and styrene 50 said styrene-acrylonitrile mixture (C)comprising (E) Styrene 78 and (F) Acrylonitrile 22 and said rubberycopolymer (D) being a copolymer of (H) Butadiene and (I) Styrene 10 it{Based on the total weight of (A) plus (B) in the compo- S 1011.

1 Based on the weight of ((3) plus (D).

5 Based on the weight of (E) plus (F).

A Based on the weight of (H) plus (I).

20. A polyvinyl chloride sheet material having the composition of claimI.

21. A molded article having the composition of claim 1.

References Cited in the file of this patent UNITED STATES PATENTS2,636,866 Barres et al Apr. 28, 1953

1. A COMPOSITION COMPRISING BLENDED WITH (B) A GRAFT COPOLYMER OF ASTYRENE-ACRYLONIBASED ON THE TOTAL WEIGHT OF (A) PLUS (B) IN THECOMPOSITION. SAID VINYL CHLORIDE RESIN (A) BEING SELECTED FROM THE GROUPCONSISTING OF HOMOPOLYMERS OF VINYL CHLORIDE AND COPOLYMERS THEREOF WITHOTHER UNSATURATED COMPOUNDS